Azo dyes and methods for their preparation



Patented July 3, 1934 AZO DYES AND METHODS FOR THEIR PREPARATION Arthur Rowan Murphy, Penns Grove, N. J., as-

signor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application January 21, 1933, Serial No. 652,927

16 Claims.

This invention relates to new azo dyes and more particularly refers to trisazo dyes having the following general formula:

sodium salt was dissolved in 2 liters water with 40 grams sodium hydroxide. It was diazotized at 10 C. by adding 91 grams hydrochloric acid wherein .R....and R represent aromatic nuclei which may be further substituted, R represents a naphthol-sulfonic acid nucleus, X represents alkyl or aromatic radicals whichmay be dissimilar, and Y represents hydrogen or anamino- 5 benzoyl nucleus; and methods for their production.

It is an object of the present invention to produce azo dyes having excellent stability to washing and light. A further object is to proii) 'duce azo dyes which impart bright attractive colors to cotton, particularly in the various shades of green. A still further object is to produce dyes which may be developed on the fiber, and which may readily be discharged. Additional objects will appear hereinafter.

These objects are attained by the present in- 'vention wherein a diazotized aromatic amino-azo compound is coupled with an amino-hydroquinone ether, the resulting amino-disazo compound being diazotized and coupled with an aminobenzoyl-amino-naphthol-sulfonic acid or an amino benzyl amino benzoyl amino-naphthol- S OaNa S OaNa stood by reference to the following illustrative examples:

Example 1 275 grams of aniline-2-5-disulfonic acid mono- NHY (100%) and 69 grams sodium nitrite. To this solution was added a solution of 245 grams 1- naphthylamine-'7-sodium-sulfonate in 5 liters water. After the coupling was completed the amino-azo compound was diazotized at -15 C. by addingQl gramshydrochloric acid (100%) and 69 grams sodium nitrite. To this diazonium compound was added a solution of 153 grams aminohydroquinone-dimethyl-ether and 36 grams hydrochloric acid (100%) in 2.5 liters water, and then 272 grams sodium acetate crystals were added. After stirring several hours the solution was cooled to 5 C. and diazotized with 91 grams hydrochloric acid (100%) and 69 grams sodium nitrite. This diazo compound was then run into a solution of 376 grams para-amino-benzoyl-Z- amino-5-naphthol-7-sulfonic acid and 17.0 grams ammonia in 3 liters water cooled to 0 C. with ice. After the coupling was completed the solution was warmed to 40 C. and saturated with salt to .precipitatexthe dye which was then filtered and dried. The following formula represents its constitution:

OCH; OH

NH-o OONH,

SOsH

erties. color in its free acid form is probably:

The constitution of the green developed until coupling was completed. The amino-azo compound was then dissolved with 100 grams so- SOZH OCH; OH

O;H CH3 NHCO N==N(|}H III- l CZN S0311 SOaH L Example 2 dium hydroxide and diazotized at 2025 C. by

325 grams of the mono-sodium salt of 2-naphthylaminel-s-disulfonic acid was dissolved in 2 liters water with 40 grams sodium hydroxide, and diazotized at 10-l5 C. by adding 91 grams hydrochloric acid (100%) and 69 grams sodium nitrite. To this solution was added 245 grams 1 naphthylamine-7-sodium-sulfonate dissolved in liters water After the coupling was completed the amino-azo compound was diazotized at 2530 C. by adding '73 grams hydrochloric acid (100%) and 69 grams sodium nitrite. This diazonium compound was cooled at C. and the excess mineral acid was neutralized with 70 grams sodium acetate crystals. There was added to it a suspension of amino-hydroquinone-dimethyl-ether made by dissolving 153 grams in 2.5 liters water with 37 grams hydrochloric acid 1 (100%) and precipitating with 140 grams sodium acetate crystals. After the coupling was com pleted this disazo compound was diazotized with 145 grams hydrochloric acid (100%) and 7 6 grams sodium nitrite. After stirring one hour at 10 C.

O :Na CH;

OgNa

" The precipitate was filtered oil and dried. The

constitution of this product is represented by the following formula:

S OsNB @WQQMMQMM S0;Na SOaNa This dyestuff was similar in properties to the one given in example 1, and the developed dye was of about the same shade.

Example 3 181 grams amino-terephthalic acid was dissolved in 2 liters water with 80 grams sodium hydroxide. It was cooled to 10 C. and diazotized with 128 grams hydrochloric acid (100%) and 69 grams sodium nitrite, and then neutralized to Congo red with '70 grams sodium acetate. To this diazonium compound was added a solution of 245 grams 1-naphthylamine-7-sodium-sulfonate in 5 liters water, and the mixture was stirred at C.

adding 200 grams hydrochloric acid (100%) and 69 grams sodium nitrite. The diazonium compound was neutralized with 70 grams sodium acetate crystals and coupled with 153 grams aminohydroquinone-dimethyl-ether, which had been dissolved in 2.5 liters water with 37 grams hydrochloric acid (100%) and precipitated with 140 grams sodium acetate crystals. After the coupling was completed the disazo compound was filtered and redissolved in 10 liters water and 106 grams sodium carbonate. It was cooled to 10 C. and diazotized by adding 240 grams hydrochloric acid (100%) and 69 grams sodium nitrite. After one hour the insoluble diazonium compound was poured into a solution of 376 grams para-aminobenzol-la-mino-8-naphthol-4sulfonic acid and 170 grams ammonia in 3 liters water cooled with ice to 0 C. The solution was then saturated with salt, stirred several hours, and the precipitated color was filtered off and dried. The following formula is a graphical representation of its constitution:

on NH-C OQ-NH:

OCH;

The direct cotton dyeing of this product was a greener-blue than was obtained from the products obtained in the first two examples, and after diazotization and development with lphenyl-3-methyl-5-pyrazolone, it gave a yellower-green of similar properties.

It is to be understood that the present invention is capable of wide variation and modification in the manner of its practical application. For example, in place of the first component,

OCH; OH

represented by R in the general formula heretofore given, other aromatic amines may be used and these amines may have substituted thereon alkyl, halogen, alkoxy, sulfonic. acid, carboxylic acid, nitro and related groups. Among these amines are G-chlor-aniline-3-sulfonic acid, 5- chlor-aniline-2-sulfonic acid, 2-amino-4-sulfobenzoic acid, 2-chlor-5-amino-4-sulfo-benzoic acid, 5-nitro-aniline-2-sulfonic acid, and 1- amino-S-naphthol-S-6-disulfonic acid.

The second component is an aromatic amine which couples para to the amino group, and which may have additional groups substituted thereon. Alpha-naphthylamine-sulfonic acids S OgNB Cab ftime of reaction and proportions of which couple in the 4-position are preferred for this component, although the invention is not limited thereto. Compounds which fall within this class and which have been used with satisfactory results are l-naphthylamine-2-sulionic acid, 1-naphthylamine-7-sulfonic acid, Z-methoxy-l-naphthylamine-fi-sulfonic acid, Z-ethoxy- 1-naphthylamine-6 su1ionic acid, and 2-methoxy-l-naphthylamine-7-sulionic acid.

The third component is an amino-hydroquinone-ether, either aliphatic or aromatic others being suitable, although the alkyl others are preferred. These ethers may be the same or dissimilar, and they may belong to either the aliphatic or aromatic series or they may belong to both series. It may here be mentioned that amino-hydroquinone-dimethyl-ether is preferred, although other ethers such the diethyl-ether and dibenzyl-ether give satisfactory results. This component may have additional groups, for example alkyl groups, substituted thereon.

The end component is an amino-benzoyl-aminc-naphthol-sulfonic acid or an amino-benzoylamino-benzoylamino-nap thol sulfonic acid, wherein the amino groups may occupy difierent positions on the benzoyl nucleus, the J- acid, S-acid and Macid derivatives eing preferred. Examples of such compounds are paraamino benzoyl J acid, para amino-benzoylj, para amino benzoyl-J-acid, meta-ainino-benzoyl J -acid, meta--amino-benzoyl-meta-amino benzoyl J-acid, para-amino-benZoyl-meta-amino-benzoyl-J-acid, para-amino-benzoyl-S-acid, and meta-amino-benzoyl-M-acid. Where a yeljlow shade of green is desired the S-acid derivatives appear to be preferable. On the other hand,'the J -acid derivatives have been found to produce colors which are somewhat faster to washing.

As is well known J -acid is 2-amino-5-hydroxy- '7-su1fonic acid, S-acid is 1-amino-8-hydroXy-4- sulionic acid and M-acid is l-amino-5hydroxy l-sulfonic acid.

The several factors such as temperature,

reacting substances may also be varied within rather wide limits without departing from the scope of the present invention. In addition, the customary means whereby undesirable side reactions are eliminated or greatly reduced may be impart attractive colors to cotton, particularly desirable shades of green. Moreover, the imparted colors may be discharged from the material quite readily and effectively. The shades produced are much brighter and more attractive than those produced from somewhat related compounds, apparently due to the presence of tlie amino-hydroquinone-ether componen v As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it

is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A process for producing azo dyes which comprises coupling a diazotized aromatic amino-azo compound with an amino-hydroquinone-ether, diazotizing the resulting amino-disazo compound and coupling it with a Irernber selected from the group consisting of amino-benzoyl-amino-naphthol-sulfonie. acids and amino-benzoyl-ainino benzoyl-amino-naphthol-sulionic acids.

2. A process for producing azo dyes which comprises coupling a diazotized aromatic amino-azo compound the components or" which are members of the benzene or naphthalene series with an amino-hydroquinone-alkyl-ether, diazotizing the resulting amino-disazo compound and coupling it with a member selected from the group consisting of amino-benzoy1-amino-naphthol-sulfonic acids and amino-benzoyl-amino-benzoylamino-naphthol-sulfonic acids.

3. A process for producing azo dyes which coinprises coupling a diazotized aromatic amine of the benzene or naphthalene series which may have substituted thereon members selected from the group consisting of alkyl, halogen, alkoxy, sulfonic, carboxylic and nitro radicals, with an alpha-naphthylamine-sulfonic acid which coupies in the position para to the amino group, diazotizing the resulting amino-azo compound and coupling it with amino-hydroquinOne-dimethyl-ether, diazotizing the resulting aminodisazo compound and coupling it with a mom-- ber selected from the group consisting of paraamino benzoyl-, meta amino benZoyl-, paraarnino-benzoyi-paraamino-benzoyl-, meta-amamino-benzoyl-meta-amino-benzoyl-, para-amino -benzoyl-meta-amino-benzoyl-, and metaamino-benzoyl-para-amino-benZoyl-J, S, or -M acid. 4

4. A process for producing azo dyes which coinprises coupling a diazotized amino-benzene-sulionic acid which may have substituted thereon members selected from the class consisting of alkyl, halogen, alkoxy, sulfonic acid, carboxylic acid and nitro groups with a1pha-naphthylamine 6-.sulfonic acid or a1pha-naphthylamine T-sulionic acid, diazotizing the resulting amino-azo compound and coupling it with Z-S-dirnethoxyaniline, diazotizing the resulting amino-disazo compound and coupling it with a member selected from the group consisting of para-aminobenzoyl-, meta-amino-benzoyl-, para-aminobenzcyl-para-amino-benzoyl-, meta-amino-benzoyl-meta-amino-benzoyl-, para-amino-benzoylmeta-amino-benzoyL, and meta-amino-benzoyh para-amino-benzoyl-J, -S, or -M acid.

5. A process for producing azo dyes which comprises coupling a diazotized amino-benzenedisulfonic acid with alphanaphthy1arr ine-7-sulionic acid, diazotizing the resulting amino-a o compound and coupling it with 2-5-dimethoxyaniline, diazotizing the resulting amino-disazo compound and coupling it with a member selected from the group consisting of para-aminobenzoy1-, meta-amino-benz'oyh, para-aminobenzoyl-para-an1ino-benzoyl meta-amino-benzoyl-meta-amino-benzoyl-; para-amino-benzoylmeta-amino-benzoyl-, and meta-amino-benzoylpara-amiiio-benzoyl-J, -S, or -M acid.

6. A process for producing an azo dye which comprises coupling diazotiZe-d aniline-25-disulfonic acid with l-naphthylamine-7-sulfonic acid, diazotizing the resulting amino-azo compound and coupling it with amino-hydroquinone-dimethyl-ether, diazotizing the resulting aminodisazo compound and coupling it with paraamino benzoyl 2-a1nino-5naphthoi-7 sulfonic acid.

CAD

'7. A process for producing azo dye which.

comprises coupling diazotized Z-naphthylamina fonic acid, diazotizing the. resulting amino-'azo' compound and coupling it with amino-hydroaminobenzoyl-meta-amino-benzoyl-, para-amino-benzoyl-meta-amino-benzoyl-, or m e t a amino-benzoyl-para-aminobenzoyl-J, S, or M acid.

12. Azo dyes having the general formula:

OCH;

(BOH; wherein R represents the residue of an aminobenzene-sulfonic acid which may have substituted thereon members selected from the class l OX wherein R and R represent aromatic nuclei, R" represents a naphthol-sulfonic acid nucleus, X represents alkyl or aromatic radicals which may be dissimilar and Y represents hydrogen or an amino-benzoyl-nucleus.

10. Azo dyes having the following general formula:

NHY

consisting of alkyl, halogen, alkoxy, sulfonic acid, carboxylic acid and nitro groups, R represents the residue of l-naphthylamine-fi-sulfonic acid or lnaphthylamine7-sulfonic acid, and R" represents the residue of a para-aminobenzoyl-, meta-aminobenzoyl-, para-aminobenzoyl-para-amino-benzoyl-, meta-amino-benwherein R and R represent aromatic nuclei of the benzene or naphthalene series, B represents a naphthol-sulfonic acid nucleus, X represents alkyl radicals which may be dissimilar, and Y represents hydrogen or an amino-benzoyl nucleus.

11. Azo dyes having the following general formula:

OCH:

wherein R represents an aromatic nucleus of the benzene or naphthalene series which may have substituted thereon alkyl, halogen, alkoxy, sulfonic, carboxylic and nitro radicals, R represents the residue of an alpha-naphthylaminesulfonic acid which couples in the position para to the amino group, and R" represents the residue of a para amino-benzoyl-, meta amino benzoyl-, paraarninobenzoyl-para-aminobenzoyl-, metazoyl-meta-amino-benzoyl-, para-amino-benzoylmeta-amino-benzoyl-, or meta-amino-benzoylpara-amino-benzoyl-J, S, or M acid.

13. Azo dyes having the following general formula:

OCH;

OCH;

wherein R represents the residue of an aminobenzene-disulfonic acid, and R represents the residue of a para-amino-benzoyl-, meta-aminobenzoyl-, para-aminobenzoylpara-amino-benzoyl-, meta amino benzoyl meta amino benzoyl-, para amino benzoyl meta amino benzoyl, or meta-aminobenzoylpara-amino-benzoyl-J acid, S, or M acid.

14. An azo dye having the following formula:

SO;Na 0011, OH O N=N N=N s'oma (50113 I NH-C OONH,

S 0 Na sour 15. An azo dye having the following formula:

soma 00H. on

60H; I NH-c OONH-C CONE:

som. soma soma 16. An azo dye having the following formula:

OaNa 0 OH; OH NH-C O-ONHz 80 N= =N N:

OsNa

1D SO3N8 5 ARTHUR R. MURPHY.

CERTIFICATE OF CORRECTION.

Patent No. 1,965,201. July 3, 1934.

ARTHUR ROWAN MURPHY.

It is hereby certified that error appears in the printed specification of the above numbered, patent requiring correction as follows: Page 1 line 32, for "benzyl read benzoyl; page 2, line 103, for "benzol" read benzoyl; and page 4, line 3, claim 7, after "2-" insert amino-; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 7th day of August, A. D. 1934.

Leslie Frazer (Seal) Acting Commissioner of Patents. 

